Title: Determination of Ca2+ and Mg2+ in Water

by EDTA (Complexometric) Titration—Test for Water

Hardness
Abstract
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Kgasu Mosa
202112103
 ABSTRACT

The purpose of the study was to determine the total hardness of water using the
concepts learned about the complexometric EDTA titration. The hardness of water is
defined in terms of its content of calcium and magnesium ions, and by the
complexometric EDTA titration, which is the process of metal ion titration until a
product of complexes is obtained, hardness can be determined. There total hardness of
water was identified to categorize the use a specific type of water —whether it is
used domestically or industrially. The determination of water hardness is also a useful
test that provides a measure of quality of water for households, particularly for water
potability. The working standard CaCO3 solution was added with buffer solution and
Eirochrome Black T (EBT) indicator for the standardization of the EDTA titrant solution.
The analysis of water sample involved the titration of a measured volume of
mineralized water of the brand Hidden Spring (plus buffer solution and EBT indicator)
with the EDTA solution. A color change from wine red to clear blue indicates the
titration endpoint. The computed total hardness was 248.7 ppm (average of the three
trials), which is classified as very hard water. This proves that Hidden Spring is a
reliable source of mineral water. However, possible errors during the experiment may
have caused by the intrinsic error of the method and typical random errors including
human errors.

Aim
The main objective of the experiment is to determine the “hardness” of a sample of water by using EDTA to
determine the concentration of calcium and magnesium ions.

Introduction
Water hardness is important to fish culture and is a commonly reported aspect of water quality. It is a
measure of the quantity of divalent ions such as calcium, magnesium and/or iron in water. There are many
different divalent salts; however, calcium and magnesium are the most common sources of water hardness.
Hardness is traditionally measured by chemical titration. The hardness of a water sample is reported in
milligrams per litre (same as parts per million, ppm) as calcium carbonate (mg/l CaCO3). Calcium
carbonate hardness is a general term that indicates the total quantity of divalent salts present and does not
specifically identify whether calcium, magnesium and/or some other divalent salt is causing water hardness.
Hardness can be a mixture of divalent salts. In theory, it is possible to have water with high hardness that
contains no calcium. The determination of water hardness is a useful test that provides a measure of quality
of water for households and industrial uses. Originally, water hardness was defined as the measure of the
capacity of the water to precipitate soap. Hard water is not a health hazard. People regularly take calcium
supplements. Drinking hard water contributes a small amount of calcium and magnesium toward the total
human dietary needs of calcium and magnesium. The National Academy of Science states that consuming
extremely hard water could be a major contributor of calcium and magnesium to the diet.
The ions involved in water hardness, i.e. Ca2+(aq) and Mg2+(aq), can be determined by titration with a
chelating agent, ethylenediaminetetraacetic acid (EDTA), usually in the form of disodium salt (H2Y2-). The
titration reaction is:

Eriochrome Black T is commonly used as indicator for the above titration. At pH 10, Ca2+(aq) ion first
complexes with the indicator as CaIn+(aq), which is wine red. As the stronger ligand EDTA is added, the
CaIn+(aq) complex is replaced by the CaY2-(aq) complex which is blue. The end point of titration is
indicated by a sharp color change from wine red to blue.

Procedure
The experiment started by preparing all the needed solutions for the study. The solutions prepared were
500 mL 0.1000 M stock Ethylenediaminetetraacetic acid (EDTA) solution, 100 mL 0.0500 M stock Ca2+
solution, and a 250 mL 1.0 M NH3-NH4+ pH 10 buffer solution. To avoid confusion, the solutions will be
named solutions A, B, and C respectively.
Solution A was prepared by adding approximately 6,0009 grams of Na2H2EDTA * H2O to the nearest
0.1 milligrams in a 500 mL beaker and adding 400 mL of distilled water. Then the entire solution was
quantitatively transferred in a 500 mL volumetric flask, filling to mark with distilled water and mixing.
Next, solution B was prepared by adding approximately 0.791 grams of pure CaCO3 (with a purity of
99.97%) to a 250 mL beaker and adding 40 mL distilled water. HCl was then added to the solution as it
was being heated and at the same time gently stirred. This was done to dissolve the CaCO3 solids. Upon
dissolution, the entire solution was transferred to a 100 mL volumetric flask, diluted to mark with distilled
water and mixed.
Finally, the solution C was prepared by mixing the specified values for NH3 and NH4Cl (in this case, 57
mL of NH3 and 7.0116 grams of NH4Cl into a volumetric flask, diluted to the mark and mixed. The pH was
tested using a strip of pH paper and adjusted by either adding more acid or base to attain a pH value of
10.
Additional solutions were also prepared; 250.0 ml .0100 M working EDTA solution from .1 M EDTA and
50.0 ml .0050 M working standard Ca2+ from the .0500 M Ca2+ solution. These solutions will be labelled
as Solutions A1 and B1 respectively.
The solution A1 will be prepared by getting 25 ml from the 0.1000 M EDTA and diluting and storing it to a
specified 250 ml volumetric flask. The solution B1 was prepared by getting 5 ml of the 0.0500 M Ca2+
solution diluting and storing it to a specified 50 ml volumetric flask. Standardization of the .01 M EDTA
solution started by getting three sets of 10 mL aliquots from the .0050M CaCO3 solution. 75 mL of distilled
water was also added to each of the flasks. Three mL of the buffer solution was then added to the solution
with 6 drops of the EBT indicator before titration.
The volumes (initial and final) of the titrant were then recorded. The solution was titrated until a change in
color from wine red to a clear blue was observed. This part of the experiment was done within 3 trials.
After doing the standardization, a similar process was done for the analysis of the blank titration with
distilled water to which the same amount of hydroxylation blue indicator and titrate with the EDTA solution
were added. However, instead of 10 mL, 3 sets of 50 mL water samples were added into 3 separate 250
mL Erlenmeyer flasks before adding 3 mL of the buffer solution then titrating with the EDTA solution using
the EBT as indicator. The color change observed for both was from wine red to dark blue.

RESULTS AND DISCUSSION

During the preparation of EDTA solution, MgCl2 *6H2O crystals were added to the dissolved salt EDTA. It
was added to the solution to increase its solubility via diverse ion effect.
The fact that Mg-EDTA has a higher formation constant hence a higher tendency to form complexes than
Ca-EDTA, Mg2+ from EDTA solution can easily displace Ca2+ ions and form Mg-EDTA complex Since Ca-
EDTA has a lower Kf, formation constant, Ca-EDTA is less stable because there is a greater energy for the
complex to form, so adding more Mg2+ ions will make the endpoint sharper. On the other hand, EDTA is
essentially insoluble in water, and will only dissolve when pH is neutralized to 8. Addition of base, in this
experiment NaOH pellets, facilitates dissolution of acid form of EDTA.

Carbonate errors can cause discrepancies in pH readings so adding HCl while dissolving CaCO3 during the
solution preparation is important for all reactions between metal ions and EDTA that are pH dependent,
and for divalent ions, solutions must be kept basic (and buffered) for the reaction to go to completion [5].
Most ligands are basic and bind to H+ ions throughout a wide range of pH. Some of these H+ ions are
frequently displaced from the ligands (chelating agents) by the metal during chelate formation, so a buffer
was used to hold the pH constant. In this experiment, NH3-NH4Cl buffer was used since EBT indicator only
works when the pH is at 8 to10, whereas the buffer has a pH equal to 10 [4].
Meanwhile NaOH was present to neutralize the carboxyl groups present in the EDTA crystals and as such
increases its solubility, therefore ensuring its complete dissociation into the solution [5]
Equations (1), (2), and (3) below display the reaction process the various reactants and ions undergo to
display a color change from wine red to dark blue as well as to display a sharper endpoint for the titration
process.
H2Y2– + Ca2+ → CaY2– + 2H+ (1)
H2Y2– + Mg2+ → MgY2– + 2H+ (2)
H2Y2– + Mg-In → MgY2– + HIn2–+ H+ (3)
where Mg-In = wine red solution
and HIn2–+ = dark blue endpoint
Note how EDTA reacts to both calcium (equation (1)) and magnesium ions (equation (2)) before the
magnesium ions bind to the EBT indicator.
The concentration of the two most common hard water ions, Ca2+ and Mg2+ was then determined by
titrating the water sample with a known chelating agent, EDTA. It was standardized with CaCO3 thrice and
the resulting average concentration of EDTA is 0.0095 M. (Arun Bahl, 2016) (H.F, 1948) (Jolly, 1970) (Pinho
& Macedo, 2005)

Trial 1 2 3
Volume of working 10 10 10
Ca(II) standard, mL

Net volume EDTA, 8 8.5 8.3

mL

M EDTA .0098 .0093 .0095

Average M EDTA .0095

Titer .9566187928

𝑔 𝐶𝑎𝐶𝑂3 (100.09𝑔/𝑚𝑜𝑙)(%𝑝𝑢𝑟𝑖𝑡𝑦)
𝑀 𝑠𝑡𝑜𝑐𝑘 𝐶𝑎2+ =
𝐿𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
(𝑀𝑠𝑡𝑜𝑐𝑘 𝐶𝑎 )(𝑉𝑠𝑡𝑜𝑐𝑘 𝐶𝑎 )
𝑀𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 =
𝑉𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑

(𝑀𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 )(𝑉𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 )

𝑀𝐸𝐷𝑇𝐴 =
𝑉𝐸𝐷𝑇𝐴
𝑇 = 𝑀(𝐹𝑊)
During standardization, purple color appeared upon addition of EBT indicator compared to the expected
wine-red color of the solution. This may happen since there are no Mg2+ ions in the solution, and the
indicator only exists as wine-red complex due to the magnesium ions.

On the other hand, the water sample (Hidden Spring) was titrated with the standardized EDTA. The starting
color sample upon addition of EBT indicator was wine red due to the existence of Mg2+ ions and upon
titrating with EDTA, the color gradually changes from wine red to clear blue, indication that the endpoint is
reached, which occurs when Ca2+ ions complexes with EDTA, the same time the Mg2+ complexes with it
sequentially and the Mg-EBT complex breaks as illustrated in the equation.

When comparing the obtained values above with the theoretical values obtained from the labels indicated
in the water bottle, it can be concluded that errors were still present in the experiment, however, the
objective of the experiment was still achieved, that is to determine the total hardness of a water sample.
Theoretically, the water sample contained 25 ppm and 35 ppm of both Ca2+ and Mg2+ ions respectively;
and the calculated water hardness (CaCO3 ppm) based on these theoretical values are 62.44 ppm (from
ppm Ca) and 144.10 ppm (from ppm Mg) for a total hardness of 206.54 ppm. Experimentally, the total
hardness of water was 248.70 ppm, which according to Table 1, falls under the very hard category. This
fully supports the theoretical category of the Hidden Spring water sample to fall to the very hard category.
As mentioned, certain errors could have been committed while performing the experiment that may have
affected the overall result, primarily the ppm value of calcium carbonate. Such errors committed that could
have affected the ppm value of CaCO3 are over titration (increase in VEDTA = increase in ppm CaCO3),
the negligence to allow for EDTA to pass through the burette pre-titration (increase in ppm CaCO3 due to a
most likely diluted EDTA titrant), too much EBT indicator added (indeterminate ppm CaCO3 due to a vague
shift in color), too little EBT indicator added (increase ppm CaCO3 as the time for a color shift will be
delayed), actual pH of the solution is less than 10 (decrease ppm CaCO3 due to the possible precipitation
of metal hydroxides.) The addition of indicator before the 3 mL buffer solution to the analyte may also
affect the overall process as some of the indicator may react with the solution before the buffer can work
for an ideal set-up.

CALCULATIONS

-3
{ 9.878915223x10 M + 9.297802562x10-3M + 9.521845998x10-3M )
AVERAGE M =
𝟑
-3
= 9.566187928𝑥 10 M
CONCLUSIONS
Complexometric titration was utilized to determine the hardness of the 50 mL Hidden Spring water sample.
Water hardness is basically a set of standards used to determine whether a water sample is suitable for
domestic or industrial use. Generally, very hard water is mostly suitable for drinking and not for industrial
use for hard water can; clog pipes due to formation of precipitates called “scales /mineral deposits” when
heated, reduce the life of clothes due to the slimy film/yellow coating the “scales” form in clothes, and it can
further deteriorate the performance of appliances due to excess mineral deposits. EDTA was used as the
titrant because of its efficiency and stability in forming metal-ion complexes, specifically with the Mg2+ and
Ca2+ ions found in the water sample. Because of various disassociations and formations among the
reactants and ions involved as expressed in equations (1), (2), and (3), a color change from wine red to
dark blue may be observed to determine the MEDTA as well as the ppm CaCO3. Various errors such as
over titration, addition of indicator before buffer (for the analyte), addition of too much or too little
indicator, have influenced the accuracy of the data. Lastly, after determining the total hardness of the
water sample, and after comparing the results from the theoretical values, it can be concluded that the
Hidden Spring water sample is classified with a total hardness that falls to the category of “very hard”
which signifies its high-mineral content and potability as a type of drinking water.

Questions
1. Water is usually softened by using an ion exchange resin to replace each Ca2+ (and Mg2+) ion
with 2Na+ ions. What must be true of the Na+ salt of soap?

2. A 0.2431 g sample of CaCO3 is dissolved in 6 M HCl and the resulting solution is diluted to 250.0
mL in a volumetric flask. Titration of a 25.00 mL sample of the solution requires 28.55 mL of EDTA
to reach the Eriochrome Black T end point. A blank containing the same amount of Mg2+ requires
2.60 mL of EDTA. What is the molarity of the EDTA solution?
3. A 50.00 mL sample of hard water is titrated with the EDTA solution in Problem 2. The same amount
of Mg2+ is added as previously, and the volume of EDTA required is 22.44 mL. What is the water
hardness in ppm CaCO3?
References
Arun Bahl, B. B. (2016). Essentials of Physical Chemistry . New York: Multicolour edition.
Cohen, M. (2011). Shaping modern science (1st ed.). canada: Crabtree Publishing.
H.F, W. (1948). Inorganic Preparations. Saunders: Prentice-Hall, Inc.
Hunt, D. I. (2019). Electrophilic Aromatic Substitution. Retrieved March 21, 2022, from
http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch12/ch12-7b.html
Jolly, W. L. (1970). In The synthesis and characterization of inorganic compounds. LA: Prentice-Hall.
McMurry, J. (2016). Organic Chemistry, Ninth Edition (9th ed.). Boston, MA 02210: Parallelogram Graphics .
Pinho, S. P., & Macedo. (2005). Solubility of NaCl, NaBr, and KCl in Water. Chicago: Journal of Chemical &
Engineering Data.